Discrete Complexes and One-Dimensional Coordination Polymers with [Cu(II)(2,2’-bpy]2+and [Cu(II)(phen]2+ Corner Fragments: Insight into Supramolecular Structure and Optical Properties
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MELNIK, E., COROPCEANU, Eduard, FORNI, Alessandra, CARIATI, Elena, KULIKOVA, Olga, SIMINEL, Anatolii, KRAVTSOV, Victor, FONARI, Marina. Discrete Complexes and One-Dimensional Coordination Polymers with [Cu(II)(2,2’-bpy]2+and [Cu(II)(phen]2+ Corner Fragments: Insight into Supramolecular Structure and Optical Properties. In: Crystal Growth and Design, 2016, nr. 11(16), pp. 1275-1285. ISSN 1528-7483. DOI: https://doi.org/10.1021/acs.cgd.6b00807
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Crystal Growth and Design
Numărul 11(16) / 2016 / ISSN 1528-7483

Discrete Complexes and One-Dimensional Coordination Polymers with [Cu(II)(2,2’-bpy]2+and [Cu(II)(phen]2+ Corner Fragments: Insight into Supramolecular Structure and Optical Properties

DOI:https://doi.org/10.1021/acs.cgd.6b00807

Pag. 1275-1285

Melnik E.1, Coropceanu Eduard2, Forni Alessandra3, Cariati Elena4, Kulikova Olga1, Siminel Anatolii1, Kravtsov Victor1, Fonari Marina5
 
1 Institute of Applied Physics, Academy of Sciences of Moldova,
2 Institute of Chemistry of the Academy of Sciences of Moldova,
3 Consiglio Nazionale delle Ricerche di Italia,
4 University of Milan,
5 New Mexico Highlands University, Department of Chemistry, Las Vegas
 
 
Disponibil în IBN: 7 noiembrie 2017


Rezumat

The combination of [Cu(II)(2,2′-bpy)]2+ and [Cu(II)(phen)]2+ (2,2′-bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) corner fragments predisposed to π-π stacking interactions with bridging ligands 4,4′-bipyridine (4,4′-bpy), 4,4′-bipyridinethane (bpe), and 4,4′-bipyridinepropane (bpp) in the presence of linear SCN-, or tetrahedral ClO4 - or BF4 - inorganic anions and/or organic acetate anion provides access to a series of new metal-organic materials including non-centrosymmetric polymeric chains, whose architectures were confirmed through single crystal X-ray crystallographic analysis. The nine reported compounds comprise one mononuclear complex, [Cu(2,2′-bpy)2(CH3COO)](SCN)(H2O) (1), three binuclear complexes, [Cu2(2,2′-bpy)2(CH3COO)2(SCN)2(4,4′-bpy)]0.5dmf (2), [Cu2(phen)2(CH3COO)2(SCN)2(bpe)] (3), [Cu2(phen)2(SCN)4(bpe)] (4), and five one-dimensional coordination polymers, {[Cu(2,2′-bpy)(4,4′-bpy)(ClO4)2](H2O)}n (5), {[Cu(phen)(4,4′-bpy)(BF4)2](H2O)}n (6), {[Cu(2,2′-bpy)(ClO4)(H2O)(bpp)](ClO4)}n (7), {[Cu(phen)(ClO4)(dmf)(bpp)](ClO4)}n (8), and {[Cu(phen)(bpp)(BF4)2][Cu(phen)(bpp)2(BF4)](BF4)}n (9). Coordination polymers represent the neutral (5, 6), cationic (7, 8), or a blend of neutral and cationic chains (9), and differ by the Cu(II) coordination cores, conformations of the bridging ligands, and functions of the anions. All compounds except 7 reveal cooperative π-π stacking interactions of corner fragments. As expected for the paramagnetic d9 Cu(II) complexes, the polymeric solids show the luminescence quenching. The second order nonlinear optical properties of powders of the non-centrosymmetric compounds 8 and 9 were also tested.

Cuvinte-cheie
Chains, Coordination reactions, Ions, ligands, Negative ions, Nonlinear optics, optical properties, Organometallics, Polymers, single crystals, X ray crystallography, coordination, Polymers, Luminescence quenching, One-dimensional coordination polymer, Supramolecular structure,

Metal organic materials, Mononuclear complexes, Second-order nonlinear optical property, X-ray crystallographic analysis